WO2013078038A1 - Reconditioning glass - forming molds having a surface oxidized titanium -aluminum -nitride glass release coating - Google Patents

Reconditioning glass - forming molds having a surface oxidized titanium -aluminum -nitride glass release coating Download PDF

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Publication number
WO2013078038A1
WO2013078038A1 PCT/US2012/064914 US2012064914W WO2013078038A1 WO 2013078038 A1 WO2013078038 A1 WO 2013078038A1 US 2012064914 W US2012064914 W US 2012064914W WO 2013078038 A1 WO2013078038 A1 WO 2013078038A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
accordance
release coating
aluminum
nitride
Prior art date
Application number
PCT/US2012/064914
Other languages
English (en)
French (fr)
Inventor
Jiangwei Feng
Janet MITCHELL
Ljerka Ukrainczyk
Original Assignee
Corning Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to JP2014543494A priority Critical patent/JP6023818B2/ja
Priority to CN201280057186.3A priority patent/CN105102383A/zh
Priority to KR1020147017203A priority patent/KR20140143738A/ko
Publication of WO2013078038A1 publication Critical patent/WO2013078038A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B11/00—Pressing molten glass or performed glass reheated to equivalent low viscosity without blowing
    • C03B11/06—Construction of plunger or mould
    • C03B11/08—Construction of plunger or mould for making solid articles, e.g. lenses
    • C03B11/084—Construction of plunger or mould for making solid articles, e.g. lenses material composition or material properties of press dies therefor
    • C03B11/086—Construction of plunger or mould for making solid articles, e.g. lenses material composition or material properties of press dies therefor of coated dies
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00—Press-moulding glass
    • C03B2215/02—Press-mould materials
    • C03B2215/08—Coated press-mould dies
    • C03B2215/10—Die base materials
    • C03B2215/11—Metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B2215/00—Press-moulding glass
    • C03B2215/02—Press-mould materials
    • C03B2215/08—Coated press-mould dies
    • C03B2215/14—Die top coat materials, e.g. materials for the glass-contacting layers
    • C03B2215/22—Non-oxide ceramics

Definitions

  • Metals such as cast iron, stainless steel, copper alloys and nickel super alloys are frequently used to fabricate glass-forming molds, but most are subject to surface oxidation at temperatures above 600°C in air.
  • metals can react with alkali ions present in molten glass at typical glass-forming temperatures, producing alkali-modified mold surfaces that are increasingly glass-adherent. The resulting sticking between the glass and mold surfaces eventually degrades the surface qualities of both the molds and the glass articles being formed.
  • Alternative mold fabrication materials such as SiC, SiN, and Sialon
  • aluminosilicate glass articles with defect- free molded surfaces is the use of titanium-nitride- based (TiN) release coatings, i.e., mold surface coatings consisting predominantly of refractory coating materials such as titanium aluminum nitride (Ti-Al-N).
  • TiN titanium-nitride- based
  • Ti-Al-N titanium aluminum nitride
  • the extended glass release properties and reduced interfacial reactivities of such coatings against molten alkali aluminosilicate glasses have been found to preserve molded glass surface quality and provide closer control of dimensional tolerances for molded glass articles over somewhat longer service periods due to the higher chemical stability and good surface wear resistance of such coatings.
  • Mold replacement can offer the only solution to the sticking problem for uncoated molds, whereas in the case of coated molds, mold resurfacing methods can be used.
  • mold resurfacing methods can be used.
  • the most effective methods for resurfacing coated molds have involved removing the worn coatings, for example by machining or chemical dissolution, followed by the application of new coating layers.
  • the removal and recoating steps required to replace the exhausted coatings are time-consuming and expensive.
  • more effective and economic methods for extending the services lives of glass forming molds used for the shaping of hard, chemically aggressive glasses are needed.
  • a method for reconditioning rather than replacing a titanium aluminum nitride glass release coating disposed on the surface of a glass forming mold is provided.
  • the method derives in part from our discovery of the underlying cause of glass adherence to such coatings following repeated contact with hot alkali- containing glasses. Without intending to be bound by theory, evidence suggests that the top surface of these coatings becomes oxidized during use to form a thin but dense aluminum oxide layer.
  • That layer likely helps to retard oxygen diffusion into the coatings during use, but at the same time is found to be strongly reactive toward Na 2 0 and Si02, interacting with hot glasses during molding to form an sodium enriched aluminum silicate surface layer on the Ti-Al-N coating, this glass components enriched coating top oxide has relatively low liquidus phase and can result in glass sticking to mold coating during forming the increased coating stickiness eventually leads to degraded surface cosmetics in the molded glass articles and failure of coating .
  • a surface-oxidized titanium-aluminum-nitride -containing glass release coating disposed on the surface of a glass-forming mold is contacted with an aqueous mineral acid solution comprising a combination of fluoride and phosphate ions.
  • the surface-oxidized release coating to be contacted comprises a glass-adhering surface oxidation layer comprising oxygen, aluminum, and alkali metal.
  • the surface oxidation layer is a nitrogen-depleted layer, and/or a surface oxidation layer comprising silicon and sodium and aluminum.
  • the present invention comprises a glass-forming mold supporting a reconditioned titanium-aluminum-nitride -based release coating processed in accordance with the methods disclosed herein.
  • a reconditioned coating provided in accordance with embodiments of the present invention is substantially free of surface nitrogen depletion but comprises measurable surface concentrations of diffused alkali metal, silicon, and oxygen.
  • the present invention comprises methods for forming a glass article from an ion-exchange-strengthenable high-alkali aluminosilicate glass.
  • Those methods comprise the step of contacting and shaping the glass with a glass-forming mold having a metal mold base supporting a titanium-nitride-based glass release coating, wherein the titanium-nitride-based release coating is a reconditioned coating that is substantially free of surface nitrogen depletion but that comprises measurable surface concentrations of diffused alkali metal, silicon, and oxygen.
  • Fig. 1 is an electron photomicrograph of a Ti-Al-N-coated glass-forming mold
  • Fig. 2 is a plot of oxygen surface concentration in a Ti-Al-N glass release coating
  • Fig. 3 is a plot of diffused alkali metal surface concentration in a Ti-Al-N glass release coating
  • Fig. 4 is a plot of diffused silicon surface concentration in a Ti-Al-N glass release coating
  • Fig. 5 is a plot illustrating nitrogen depletion in a Ti-Al-N glass release coating
  • Fig. 6 plots material removal from a metal alloy glass-forming mold.
  • the methods of the present invention can be usefully applied to recondition glass release coatings employed for molding a wide variety of moldable glass compositions, they are of particular advantage for the refreshment of coatings used for the forming of high- melting ("hard") alkali aluminosilicate glasses.
  • the present methods effectively remove the out diffused alkali (e.g., sodium), alkali earth and silicon from Ti-Al-N-based release coatings that are the major cause of glass sticking in the forming of such glasses.
  • Ti-Al-N-based coatings are restored to their nearly original compositions, greatly extending coating service life and thus reducing the need for coating replacement.
  • Selected embodiments of the present invention are particularly well adapted for the restoration of glass-forming tooling comprising a metal mold base supporting a high temperature release coating composed at least predominantly of titanium- aluminum nitride (i.e., consisting of greater than 80 atomic percent total of titanium, aluminum and nitrogen), wherein the release coating comprises a glass-adhering surface oxidation layer comprising mainly oxygen, aluminum, silicon and alkali metal and other alkali earth elements.
  • the methods of the present invention are used to restore release coatings on tooling wherein the molds comprise a metal mold base fabricated of nickel-based metal alloys.
  • the molds include nickel-chromium- iron-based metal alloys such as the InconelTM alloys. Many of those alloys consist principally (at least 80% total by weight) of nickel, chromium and iron with minor additions of such other constituents as Mo, Nb, Co, Mn, Cu, and the like, a particular embodiment of such a metal mold base being one fabricated of InconelTM 718 alloy.
  • Ti-Al-N release coatings to be treated in accordance with the present disclosure may vary widely, a number of such formulations having been employed in the prior art for improving the glass release characteristics of metal glass-forming molds.
  • Coatings composed of titanium aluminum nitride alone or alloyed with minor proportions of constituents selected from the group consisting of Si, Nb, Y, and Zr have been shown to be effective to minimize interfacial reactions between metal glass-forming molds and molten glasses during high temperature forming processes, and can be successfully treated.
  • TiAIN coating top formed a self-limiting layer of oxide compose of A1203 on the top with Ti02 underneath it.
  • glass components such as Na, Si, Ca, Mg, etc. diffuse into coating top oxide, especially Si and Na. that have significant accumulation into coating oxide, leading to the formation of sodium enriched alumina silicate that has relatively lower liquidus phase.
  • FIG. 1 A release-coated metal glass-forming mold of the kind treated in accordance with embodiments of the present invention is illustrated in Fig. 1 of the drawings.
  • Fig. 1 comprises an electron photomicrograph of a cross-section of a metal glass-forming mold 10 consisting of an InconelTM 718 nickel alloy mold base 12 provided with a Ti-Al-N release coating 14 of approximately 1.7 ⁇ thickness on the mold surface.
  • the coated mold shown in Fig. 1 is a mold that has been subjected to 200 thermal glass-forming cycles in the course of molding glass articles from an alkali alummosilicate glass.
  • release coating 14 has developed a surface oxidation layer 14a of approximately 0.159 ⁇ thickness on the surface of release coating 14, that layer exhibiting significant adherence to molten alkali alummosilicate glasses.
  • alummosilicate glasses that can cause the kinds of coating degradation shown in Fig. 1 are ion-exchange-strengthenable, high-alkali alummosilicate glasses, including for example sodium alummosilicate glasses comprising at least 10% by weight of sodium.
  • Particularly useful embodiments of the methods of the present invention are those treatments that can effectively recondition degraded titanium- aluminum mold coatings employed for the molding of such glasses.
  • Figs. 2-5 of the drawings comprise graphs reflecting surface concentration profiles for selected chemical species present at shallow coating depths proximate to the exposed (oxidized) surface of a Ti- Al-N-based glass release coating before and after 60 molding cycles in contact with such a glass.
  • the species tracked in Figs. 2-5, respectively, are oxygen, silicon, sodium and nitrogen.
  • the relative concentrations of each of these species is reflected by curves plotting the relative intensities of the signals as a function of coating depth. The intensities are reported in counts per second as generated by standard SIMS (secondary ion mass spectrometry) analyses.
  • the set of SIMS curves presented in each of the Figures for each of the analyzed species includes a curve 20 reflecting species concentrations prior to exposure of the coating to molten glass, a curve 22 reflecting concentration in the surface-oxidized coating following exposure to 60 glass molding cycles, and curves 1, 2, 3, 4 and 5 reflecting, respectively, the species concentrations following treatment of the surface- oxidized coating by one of 5 different treatment methods.
  • Those methods, with numbers corresponding to the drawing curves, are as follows:
  • Method 1 Exposure to a KOH based detergent (pH 13) in an ultrasonic bath at 60°C for 15 minutes;
  • Method 2 Soaking in 120°C 45% KOH for 15 min, and then room temperature 5% HC1 for 40 minutes;
  • Method 3 Soaking in a mixture of 10 ml HC1, 150 ml H 3 P0 4 and 10 ml HF at 70°C for 15 minutes;
  • Method 4 Soaking in a mixture of 10 ml HC1, 10 ml HF and 180 ml DI water at room temperature for 30 minutes;
  • Figs. 3 and 4 of the drawings reflect the extent of silicon and alkali migration into the oxidized Ti-Al-N-based coating.
  • Curve 22 in Fig. 4 indicates a sodium concentration in the cycled coating that is approximately two orders of magnitude higher within a coating depth of 70 nm than is seen in the as-applied coating of curve 20, that sodium being largely concentrated in the oxidized layer indicated in Fig. 2.
  • a similar increase in silicon concentration in the oxidized coating surface is indicated by curves 20 and 22 in Fig. 3 of the drawings.
  • Method 4 is relatively ineffective for reducing surface oxygen levels and reversing surface nitrogen depletion.
  • Method 3 involving the use of an acid solution comprising both fluoride and phosphate ions produces a reconditioned coating surface most closely approximating an as-applied release coating in terms of oxygen, silicon and alkali levels, while at the same time effectively addressing nitrogen depletion in the reconditioned coating surface.
  • acid solutions comprising a combination of H 3 PO 4 , HC1 and HF have been found to be unexpectedly effective in both removing surface contamination and restoring the glass-release properties of Ti-Al-N-based release coatings such as herein described.
  • Release coatings treated with acidic solutions comprising these three acids are clearly distinguishable from both newly-deposited titanium-aluminum-nitride-based release coatings and exhausted (surface-oxidized) coatings exhibiting high surface concentrations of alkali, silicon and oxygen contaminants.
  • reconditioned coatings provided in accordance with these embodiments comprise detectable subsurface concentrations of diffused alkali metal, silicon, and oxygen that are not present in freshly applied nitride release coatings, although the coatings nevertheless exhibit excellent glass release characteristics notwithstanding the presence of these concentrations.
  • exhausted or surface- oxidized nitride release coatings such as characterized by Curves 22 in Figs.
  • reconditioned release coatings provided in accordance with the above-disclosed embodiments are substantially free of surface and subsurface nitrogen depletion as shown by Curve 3 in Fig. 5 of the drawings.
  • a reconditioned nitride release coating is substantially free of nitrogen depletion if, as typified by Curve 3 in Fig. 5, SIMS analysis of the coating evidences no systematic difference in nitrogen concentration as between the coating surface and coating subsurface regions within 200 nm of that surface, within the measurement accuracy of the analysis.
  • a further advantage of acidic reconditioning solutions comprising a combination of fluoride and phosphate ions, in further combination with optional chloride ions, is a reduced tendency to attack metal mold base materials. Minimizing mold base material loss is important in order to avoid changes in mold shape during reconditioning. Significant material loss can result in mold configuration changes that are not acceptable where shape precision in a molded glass product is required.
  • Fig. 6 of the drawings compares chloride-fluoride- phosphate reconditioning solutions with both KOH detergent solutions and acidic HC1 and HC1-HF etching solutions in terms of the damage to an InconelTM 718 metal alloy mold base material inflicted by dissolution in these solutions. Fluoride-chloride -phosphate solutions were found to be markedly superior to the other candidate reconditioning solutions for avoiding mold base material loss during release coating reconditioning.
  • Table 1 compares the efficiencies of various acidic fluoride-chloride-phosphate treating solutions for removing surface oxide material from oxidized nitride release coatings. The comparison is terms of the step height between treated and untreated sections of the coatings exposed to the solutions. Table 1 - Etching Step Height During Mold Coating Reconditioning

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Surface Treatment Of Glass (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Glass Compositions (AREA)
PCT/US2012/064914 2011-11-23 2012-11-14 Reconditioning glass - forming molds having a surface oxidized titanium -aluminum -nitride glass release coating WO2013078038A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2014543494A JP6023818B2 (ja) 2011-11-23 2012-11-14 表面酸化された窒化チタンアルミガラス離型コーティングを有するガラス成形鋳型の再調整
CN201280057186.3A CN105102383A (zh) 2011-11-23 2012-11-14 对具有表面氧化的氮化钛-铝玻璃脱模涂层的玻璃成形模具进行重整
KR1020147017203A KR20140143738A (ko) 2011-11-23 2012-11-14 표면 산화된 티타늄-알루미늄-질화물 유리 이형 코팅을 구비한 재생 유리-형성 몰드

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161563192P 2011-11-23 2011-11-23
US61/563,192 2011-11-23

Publications (1)

Publication Number Publication Date
WO2013078038A1 true WO2013078038A1 (en) 2013-05-30

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US (1) US20130125590A1 (enrdf_load_stackoverflow)
JP (1) JP6023818B2 (enrdf_load_stackoverflow)
KR (1) KR20140143738A (enrdf_load_stackoverflow)
CN (1) CN105102383A (enrdf_load_stackoverflow)
TW (1) TWI549917B (enrdf_load_stackoverflow)
WO (1) WO2013078038A1 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10077208B2 (en) 2014-03-13 2018-09-18 Corning Incorporated Glass article and method for forming the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140224958A1 (en) * 2013-02-11 2014-08-14 Corning Incorporated Coatings for glass-shaping molds and glass-shaping molds comprising the same
TW201739704A (zh) * 2016-01-20 2017-11-16 康寧公司 塑形玻璃基材料之具高溫用途之塗層之模具
KR102558050B1 (ko) * 2016-08-05 2023-07-21 엘지전자 주식회사 3차원 형상 글래스 제조방법
CN114702235B (zh) * 2022-03-28 2024-01-26 维达力实业(深圳)有限公司 防眩光玻璃及其制备方法和显示装置
CN114605058B (zh) * 2022-03-28 2024-01-26 维达力实业(深圳)有限公司 热转印模具和防眩光玻璃的制备装置

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10077208B2 (en) 2014-03-13 2018-09-18 Corning Incorporated Glass article and method for forming the same
US10710927B2 (en) 2014-03-13 2020-07-14 Corning Incorporated Glass article and method for forming the same

Also Published As

Publication number Publication date
US20130125590A1 (en) 2013-05-23
JP6023818B2 (ja) 2016-11-09
JP2015516928A (ja) 2015-06-18
KR20140143738A (ko) 2014-12-17
TWI549917B (zh) 2016-09-21
CN105102383A (zh) 2015-11-25
TW201331144A (zh) 2013-08-01

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